US20240059962A1 - Central chirality induced spiro chiral tetradentate cyclometalated platinum (ii) and palladium (ii) complex-based circularly polarized luminescence material and application thereof - Google Patents

Central chirality induced spiro chiral tetradentate cyclometalated platinum (ii) and palladium (ii) complex-based circularly polarized luminescence material and application thereof Download PDF

Info

Publication number
US20240059962A1
US20240059962A1 US18/484,200 US202318484200A US2024059962A1 US 20240059962 A1 US20240059962 A1 US 20240059962A1 US 202318484200 A US202318484200 A US 202318484200A US 2024059962 A1 US2024059962 A1 US 2024059962A1
Authority
US
United States
Prior art keywords
mmol
equiv
circularly polarized
complex
room temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
US18/484,200
Other languages
English (en)
Inventor
Guijie Li
Yuanbin SHE
Hua Guo
Kewei Xu
Shun Liu
Feng ZHAN
Jianfeng Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Huaxian Photoelectricity Technology Co Ltd
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang Huaxian Photoelectricity Technology Co Ltd
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Huaxian Photoelectricity Technology Co Ltd, Zhejiang University of Technology ZJUT filed Critical Zhejiang Huaxian Photoelectricity Technology Co Ltd
Publication of US20240059962A1 publication Critical patent/US20240059962A1/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/62—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings
    • C07D263/64—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems having two or more ring systems containing condensed 1,3-oxazole rings linked in positions 2 and 2' by chains containing six-membered aromatic rings or ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/135—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising mobile ions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/346—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1022—Heterocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission

Definitions

  • the disclosure relate to a circularly polarized luminescence material and application thereof, in particular to a central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material and application thereof.
  • Circularly polarized luminescence is a phenomenon that chiral luminescence materials are excited and emit left-handed or right-handed circularly polarized light. Therefore, design and development of chiral luminescence materials are the key to this field. With in-depth researches by researchers, circularly polarized luminescence materials exhibit important applications in 3D display, data storage, quantum computing, optical anti-counterfeiting, biological imaging and asymmetric synthesis so far.
  • Cyclometalated platinum (II) and palladium (II) complex-based phosphorescent material can fully utilize all of singlet and triplet excitons generated by electroexcitation due to its heavy atom effect, so that its maximum theoretical quantum efficiency can be up to 100%, and thus such complex is an ideal luminescence material.
  • Bidentate cyclometalated platinum (II) and palladium (II) complexes have relatively low rigidity, and its luminescent quantum efficiency is reduced due to a fact that two bidentate ligands are easy to twist and vibrate so that energy of material molecule with an excited state is consumed in a non-radiation mode (Inorg. Chem. 2002, 41, 3055).
  • tridentate ligand-based cyclometalated platinum (II) and palladium (II) complexes can be with improved luminescence quantum efficiency due to enhanced molecular rigidity (Inorg. Chem. 2010, 49, 11276)
  • a second unidentate ligand such as Cl ⁇ , phenoxy negative ions, alkyne negative ions, carbene and the like contained greatly reduces chemical stability and thermal stability of the complexes, which is difficult to sublimate and purify for preparation of OLED devices. Therefore, the luminescence material base on that bidentate and tridentate ligand-based cyclometalated complexes do not facilitate their application in stable and efficient OLED devices.
  • Central metal ions of divalent cyclometalated platinum (II) and palladium (II) complexes are all dsp 2 hybridized, and are easy to coordinate with the tetradentate ligand to form stable and rigid molecules with a planar quadrilateral configuration.
  • High molecular rigidity can inhibit nonradiative relaxation caused by molecular vibration and rotation, and reduce energy loss of material molecules with the excited state, thereby facilitating improving of the luminescent quantum efficiency of the material molecules.
  • Due to steric hindrance of two aryl groups at an end of a tetradentate cyclometalated platinum (II) and palladium (II) complex material molecules exhibit a distorted quadrilateral configuration (Chem. Mater.
  • a central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material and application thereof are provided in this disclosure.
  • Spiro chiral metal complex molecules can autonomously induce a whole tetradentate ligand to coordinate with metal ions in a less sterically hindered manner by means of a central chiral fragment L a in the tetradentate ligand, to form an optically pure spiro chiral metal complex-based circularly polarized luminescence material, without need for chiral resolution.
  • the material has high chemical stability and thermal stability, and has important applications in circularly polarized luminescence devices.
  • An object of the disclosure can be achieved by following technical schemes.
  • a central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material is characterize by having a chemical formula as shown in general formulas (I), (I′), (II), (II′), (III) and (III′).
  • (I) and (I′), (II) and (II′), (III) and (III′) are enantiomers of each other.
  • M is Pt or PD; and V 1 , V 2 , V 3 and V 4 are independently N or C.
  • L 1 , L 2 and L 3 are each independently a five or six membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; and L a and L b are each independently a five-membered central chiral carbocyclic or heterocyclic ring. Due to steric hindrance between L a and L 1 , L a and L b , the metal complex is in a non-planar configuration as a whole, and the central chiral L a can autonomously induce formation of a spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex with metal as a center in a less sterically hindered manner.
  • II spiro chiral tetradentate cyclometalated platinum
  • II palladium
  • a 1 , A 2 , X and X 1 are each independently O, S, CR x R y , C ⁇ O, SiR x R y , GeR x R y , NR z , PR z , R z P ⁇ O, AsR z , R z As ⁇ O, S ⁇ O, SO 2 , Se, Se ⁇ O, SeO 2 , BH, BR z , R z Bi ⁇ O or BiR z .
  • R 1 , R 2 and R 3 each independently represent mono-, di-, tri- or tetra-substituted or unsubstituted, and meanwhile, R 1 , R 2 , R 3 , R a , R b , R c , R d , R e , R f , R g , R h , R x , R y and R z are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, al
  • R 1 , R 2 and R 3 Two or more adjacent R 1 , R 2 and R 3 can be selectively connected to form a fused ring; any two of R a , R b , R c and R d can be connected to form a cyclic system, and any two of R e , R f , R g and R h can be connected to form a cyclic system.
  • the central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material described above having the general formulas (I), (I′), (II) and (II′) can be with one of following general formulas: (I-A), (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H), (I-I), (II-A), and its enantiomer can be with one of following general formulas: (I′-A), (I′-A), (I′-B), (I′-C), (I′-D), (I′-E), (I′-F), (I′-G), (I′-H), (I′-I), (II′-A), which is not limited thereto.
  • M is Pt or PD; and V 1 , V 2 , V 3 and V 4 are independently N or C.
  • L 1 , L 2 and L 3 are each independently a five or six membered carbocyclic, heterocyclic, aromatic or heteroaromatic ring; and L a is a five-membered central chiral carbocyclic or heterocyclic ring.
  • the metal complex Due to steric hindrance between L a and L 1 , the metal complex is in a non-planar configuration as a whole, and formation of a spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex with metal as a center in a less sterically hindered manner can be autonomously induced the central chiral L a .
  • a 1 , X, Z and Z 1 are each independently O, S, CR x R y , C ⁇ O, SiR x R y , GeR x R y , NR z , PR z , R z P ⁇ O AsR z , R z As ⁇ O, S ⁇ O, SO 2 , Se, Se ⁇ O, SeO 2 , BH, BR z , R z Bi ⁇ O or BiR z .
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent mono-, di-, tri- or tetra-substituted or unsubstituted, and meanwhile, R 1 , R 2 , R 3 , R 3 , R 4 , R 5 , R a , R b , R c , R d , R x , R y and R z are each independently hydrogen, deuterium, halogen, alkyl, cycloalkyl, aryl, heteroalkyl, heterocycloalkyl, heteroaryl, haloalkyl, haloaryl, haloheteroaryl, alkoxy, aryloxy, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, nitro, cyano, amino, mono- or dialkylamino, mono- or diarylamino, ester, nitrile, isonitrile, heteroaryl, al
  • R 1 , R 2 , R 3 , R 4 and R 5 can be selectively connected to form a fused ring; any two of R a , R b , R c and R d can be connected to form a cyclic system.
  • L a and L b in structures of the general formulas of the central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material can be of, but not limited to, following structures:
  • L a and L b described above may further be specifically of, but not limited to, following structures:
  • the central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material is preferably selected from a group consisting of:
  • the central chirality induced spiro chiral tetradentate cyclometalated complex-based circularly polarized luminescence material can be selected from following platinum (II) metal complexes and corresponding isomers thereof and corresponding metal palladium (II) complexes thereof:
  • the central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material is applied to an organic light emitting device.
  • the organic light emitting device is an organic light emitting diode, a light emitting diode, or a light emitting electrochemical cell.
  • the organic light emitting device includes a first electrode, a second electrode and at least one organic layer provided between the first electrode and the second electrode.
  • the organic layer includes the central chirality induced spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex-based circularly polarized luminescence material.
  • the organic light emitting device is a 3D display device, a three-dimensional imaging device, an optical information encryption device, an information storage device, a biological imaging device, or the like.
  • the disclosure includes following beneficial effects.
  • the central chiral L a can independently induce the whole tetradentate ligand to coordinate with a metal ion in a less sterically hindered manner so as to form the optically pure spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex circularly polarized luminescence material with the metal ion as a center, as shown in FIG. 1 .
  • Circularly polarized luminescence material of two corresponding optically pure chiral isomers of the spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex can be conveniently prepared from the two optically pure chiral tetradentate ligands, which greatly reduces preparation cost of the material without separation and purification through a chiral column.
  • the designed and developed tetradentate ligand can well coordinate with dsp 2 hybridized platinum (II) and palladium (II) metal ions to form molecules with a stable and rigid quadrilateral configuration, with high chemical stability; meanwhile, since large steric hindrance effect exists between the designed central chiral ligand L a and the ligand L 1 or L b at another end, the metal complex molecule as a whole can form a stable spiro chiral tetradentate cyclometalated complex, so that the spiro chiral tetradentate cyclometalated complex can not be racemized and lose circularly polarized luminescence property in a solution or in a process of sublimation at a high temperature.
  • FIG. 1 shows a design idea of an optically pure spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex circularly polarized luminescence material with metal ion as a center;
  • plot (A) is a front view of a X-ray diffraction single crystal structure of an optically pure spiral chiral material (R, S)-M-PtLA1;
  • plot (B) is a top view of the X-ray diffraction single crystal structure of the optically pure spiral chiral material (R, S)-M-PtLA1;
  • plot (C) is a front view of a molecular structure of (R, S)-M-PtLA1 optimized by Density Functional Theory (DFT) computation
  • plot (D) is a top view of the molecular structure of (R, S)-M-PtLA1 optimized by Density Functional Theory (DFT) computation
  • plot (E) is a front view of a molecular structure of (S, R)-P-PtLAT optimized by DFT computation
  • plot (F) is a top view of the molecular structure of (S, R)-P-PtLAT optimized by DFT computation;
  • plot (A) is a front view of a molecular structure of (R, S)-M-PtLB3 optimized by DFT computation
  • plot (B) is a top view of the molecular structure of (R, S)-M-PtLB3 optimized by DFT computation
  • plot (C) is a molecular structure of (R, S)-M-PtLB3
  • plot (D) is a front view of a molecular structure of (S, R)-P-PtLB3 optimized by DFT computation
  • plot (E) is a top view of the molecular structure of (S, R)-P-PtLB3 optimized by DFT computation
  • plot (F) is a molecular structure of (S, R)-P-PtLB3;
  • plot (A) is a front view of a molecular structure of (R, S)-M-PtLH1 optimized by DFT computation
  • plot (B) is a top view of the molecular structure of (R, S)-M-PtLH1 optimized by DFT computation
  • plot (C) is a molecular structure of (R, S)-M-PtLH1
  • plot (D) is a front view of a molecular structure of (S, R)-P-PtL H1 optimized by DFT computation
  • plot (E) is a top view of the molecular structure of (S, R)-P-PtL H1 optimized by DFT computation
  • plot (F) is a molecular structure of (S, R)-P-PtL H1;
  • plot (A) is a front view of a molecular structure of M-PtLIII-1 optimized by DFT computation
  • plot (B) is a top view of the molecular structure of M-PtLIII-1 optimized by DFT computation
  • plot (C) is a front view of a molecular structure of P-PtLIII-1 optimized by DFT computation
  • plot (E) is a top view of the molecular structure of P-PtLIII-1 optimized by DFT computation
  • FIG. 6 is an emission spectrum of optically pure (R, S)-M-PtLAT and (S, R)-P-PtLA1 in dichloromethane at a room temperature;
  • FIG. 7 is an emission spectrum of optically pure (R, S)-M-PtLA2 and (S, R)-P-PtLA2 in dichloromethane at a room temperature;
  • FIG. 8 is an emission spectrum of optically pure (R, S)-M-PtLA3 and (S, R)-P-PtLA3 in dichloromethane at a room temperature;
  • FIG. 9 is an emission spectrum of optically pure (R, S)-M-PtLAN and (S, R)-P-PtLAN in dichloromethane at a room temperature;
  • FIG. 10 is an emission spectrum of optically pure (R, S)-M-PtLH1 and (S, R)-P-PtLH1 in dichloromethane at a room temperature;
  • FIG. 11 is an emission spectrum of optically pure (S, R)-P-PtLC3 and P-PtLIII-1 in dichloromethane at a room temperature;
  • FIG. 12 is an emission spectrum of optically pure M-PdLA1 and P-PdLA1 in dichloromethane at a room temperature;
  • FIG. 13 is an emission spectrum of optically pure M-PtLB1 and P-PtLB1 in dichloromethane at a room temperature;
  • FIG. 14 is an emission spectrum of optically pure M-PtLC1 and P-PtLC1 in dichloromethane at a room temperature;
  • FIG. 15 is an emission spectrum of optically pure M-PtLD1 and P-PtL1 in dichloromethane at a room temperature;
  • FIG. 16 is an emission spectrum of optically pure M-PtLE1 and P-PtLE1 in dichloromethane at a room temperature;
  • FIG. 17 is an emission spectrum of optically pure M-PtLF1 and P-PtLF1 in dichloromethane at a room temperature;
  • FIG. 18 is an emission spectrum of optically pure(R, S)-M-PtLK1 and (S, R)-P-PtL K1 in dichloromethane at a room temperature;
  • FIG. 19 is an emission spectrum of optically pure M-PtL1 and P-PtL1 in dichloromethane at a room temperature;
  • FIG. 20 is an emission spectrum of optically pure M-PtL3 and P-PtL3 in dichloromethane at a room temperature;
  • FIG. 21 is a circular dichroism (CD) spectrum of (S, R)-P-PtLA1 and (R, S)-M-PtLA1 in dichloromethane;
  • FIG. 22 is a circular dichroism (CD) spectrum of P-PtOO and M-PtLOO in dichloromethane;
  • FIG. 23 is a circular dichroism (CD) spectrum of (S, R)-P-PtLA3 and (R, S)-M-PtLA3 in dichloromethane;
  • FIG. 24 is a circular dichroism (CD) spectrum of (S, R)-P-PtLJ1 and (R, S)-M-PtLJ1 in dichloromethane;
  • FIG. 25 is a circular dichroism (CD) spectrum of P-PtLB3 and M-PtL B3 in dichloromethane;
  • FIG. 26 is a circularly polarized luminescence spectrum (CPL) of P-PtOO, M-PtLOO, and their mixtures at an equivalent dose in dichloromethane;
  • FIG. 27 is a circularly polarized luminescence spectrum (CPL) of (S, R)-P-PtLAT and (R, S)-M-PtLA1 in dichloromethane;
  • FIG. 28 is a circularly polarized luminescence spectrum (CPL) of (S, R)-P-PtLA3 and (R, S)-M-PtLA3 in dichloromethane;
  • FIG. 29 is a circularly polarized luminescence spectrum (CPL) of optically pure M-PtL1 and P-PtL1 in dichloromethane at a room temperature;
  • CPL circularly polarized luminescence spectrum
  • FIG. 30 is a circularly polarized luminescence spectrum (CPL) of (S, R)-P-PtLA3 and (R, S)-M-PtLA3 in dichloromethane;
  • FIG. 31 is a circularly polarized luminescence spectrum (CPL) of (S, R)-P-PtLJ1 and (R, S)-M-PtLJ1 in dichloromethane;
  • FIG. 32 is a circularly polarized luminescence spectrum (CPL) of P-PtLB3 and M-PtL B3 in dichloromethane;
  • FIG. 33 is a circularly polarized luminescence spectrum (CPL) of P-PtLB9 and M-PtL B9 in dichloromethane;
  • FIG. 34 shows a high performance liguid chromatography (HPLC) spectrum of a mixture of (R, S)-M-PtLAT and (S, R)-P-PtLAT, a high performance liguid chromatography spectrum of optically pure (R, S)-M-PtLA1; a high performance liguid chromatography spectrum of optically pure (S, R)-P-PtLAT, and a high performance liguid chromatography spectrum of sublimated (R, S)-M-PtLA1 from top to bottom;
  • HPLC high performance liguid chromatography
  • FIG. 35 is a thermogravimetric analysis curve of (R, S)-M-PtLA1;
  • FIG. 36 is a structural diagram of an organic light emitting device
  • FIG. 37 shows propagation of sunlight
  • FIG. 38 shows propagation of a circularly polarized light beam.
  • a term “optional” or “optionally” as used herein means that a subsequently described event or condition may or may not occur, and that such description includes both instances in which the described event or condition occurs and instances in which it does not.
  • compositions of the present disclosure are disclosed, as well as the compositions themselves to be used in the methods disclosed in the present disclosure. These and other materials are disclosed, and it is to be understood that combinations, subsets, interactions, groups, etc. of these materials are disclosed, and that while specific references to each of various individual and general combinations and permutations of these compounds are not specifically disclosed, each of them is specifically contemplated and described. For example, if a particular compound is disclosed and discussed and many modifications that can be made to many molecules comprising the compound are discussed, each combination and permutation of the compound and possible modifications are specifically contemplated unless specifically indicated to the contrary.
  • a linking atom used in the present disclosure is capable of linking two groups, for example, linking N and C.
  • the linking atom can optionally (if valence bonds allow) attach other chemical groups.
  • an oxygen atom will not have any other chemical group attachment since once two atoms (e. g., N or C) are bonded, the valence bonds are already fully used.
  • the linking atom is carbon, two additional chemical groups can be attached to the carbon atom.
  • Suitable chemical groups include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, ⁇ O, halogen, nitro, amine, amide, mercapto, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
  • cyclic structure refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene and N-heterocyclic carbene.
  • permissible substituents include cyclic and acyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds.
  • exemplary substituents include following content.
  • the permissible substituents may be one or more, the same or different.
  • heteroatom e. g., nitrogen
  • a term “substituted” or “substituted with” encompasses an implicit condition that such a substitution conforms to permissible valence bonds of a substituted atom and the substituent, and that the substitution results in stable compounds (e. g., compounds that do not spontaneously undergo conversion (e. g., by rearrangement, cyclization, elimination, etc.)).
  • individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted) unless explicitly stated to the contrary.
  • R refers to various specific substituents. These symbols can be any substituent, not limited to those disclosed herein, which, when defined in an example as certain substituents, can also be defined in another example as some other substituents.
  • alkyl as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like.
  • the alkyl may be cyclic or acyclic.
  • the alkyl may be branched or unbranched.
  • the alkyl may also be substituted or unsubstituted.
  • the alkyl may be substituted with one or more group including, but not limit to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo and thiol as described herein.
  • a “low alkyl” is an alkyl having 1 to 6 (e.g., 1 to 4) carbon atoms.
  • alkyl generally refer to both unsubstituted and substituted alkyl.
  • substituted alkyl is also specifically mentioned in this present disclosure by determining specific substituents on the alkyl.
  • a term “halogenated alkyl” or “haloalkyl” specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine).
  • a term “alkoxyalkyl” specifically refers to an alkyl substituted with one or more alkoxy, as described below.
  • alkylamino specifically refers to an alkyl substituted with one or more amino, as described below or the like.
  • cycloalkyl refers to both unsubstituted and substituted cycloalkane moieties
  • the substituted moiety may additionally be specifically determined in the present disclosure.
  • a specifically substituted cycloalkyl may be referred to as, for example, “alkyl cycloalkyl”.
  • a substituted alkoxy may be specifically referred to as, for example, “haloalkoxy” and a specific substituted alkenyl may be, for example, “enol” or the like.
  • use of general terms such as “cycloalkyl” and specific terms such as “alkylcycloalkyl” does not imply that the general terms do not include the specific term at the same time.
  • cycloalkyl as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms consisting of at least three carbon atoms.
  • examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like.
  • heterocycloalkyl is a type of cycloalkyl as defined above and is included in meaning of the term “cycloalkyl” in which at least one ring carbon atom is substituted by a heteroatom such as, but not limited to, a nitrogen, oxygen, sulfur or phosphorus atom.
  • the cycloalkyl and heterocycloalkyl may be substituted or unsubstituted.
  • the cycloalkyl and heterocycloalkyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo and thiol as described herein.
  • polyolefin group refers to a group containing two or more CH 2 groups attached to each other.
  • the “polyolefin group” may be express as —(CH 2 ) a —, where “a” is an integer between 2 and 500.
  • alkoxy and “alkoxy group” as used herein refer to an alkyl or cycloalkyl of 1 to 30 carbon atoms bonded by ether bonds. That is, “alkoxy” may be defined as —OR 1 , where R 1 is an alkyl or cycloalkyl as defined above. “Alkoxy” further includes alkoxy polymers just described. That is, the alkoxy may be a polyether such as —OR 1 —OR 2 or —OR 1 —(OR 2 ) a —OR 3 , where “a” is an integer between 1 to 500, and R 1 , R 2 and R 3 are each independently an alkyl, a cycloalkyl, or a combination thereof.
  • alkenyl as used herein is a hydrocarbon of 2 to 30 carbon atoms with a structural formula containing at least one carbon-carbon double bond.
  • An asymmetric structure such as (R 1 R 2 )C ⁇ C(R 3 R 4 ) contains E and Z isomers. This can be inferred in a structural formula of the present disclosure in which an asymmetric olefin is present, or it can be explicitly expressed by a bond symbol C ⁇ C.
  • the alkenyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo or thiol as described herein.
  • groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo or thiol as described herein.
  • cycloalkenyl as used herein is a non-aromatic carbon-based ring of 3 to 30 carbon atoms which consists of at least 3 carbon atoms and contains at least one carbon-carbon double bond, i.e. C ⁇ C.
  • Examples of cycloalkenyl include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenoyl, cycloheptene, and the like.
  • heterocyclic alkenyl is a type of cycloalkenyl as defined above and is included in meaning of the term “cycloalkenyl” in which at least one carbon atom of the ring is substituted with a heteroatom such as, but not limited to, a nitrogen, oxygen, sulfur or phosphorus atom.
  • the cycloalkenyl and heterocyclic alkenyl may be substituted or unsubstituted.
  • the cycloalkenyl and heterocyclic alkenyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo or thiol as described herein.
  • alkynyl is a hydrocarbon having 2 to 30 carbon atoms and having a structural formula containing at least one carbon-carbon triple bond.
  • the alkynyl may be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo or thiol as described herein.
  • cycloalkynyl is a non-aromatic carbon-based ring that contains at least 7 carbon atoms and contains at least one carbon-carbon triple bond.
  • examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like.
  • heterocyclic alkynyl is a cycloalkenyl as defined above and is included within meaning of the term “cycloalkynyl” in which at least one of the carbon atoms of the ring is replaced by a heteroatom such as, but not limited to, a nitrogen, oxygen, sulfur or phosphorus atom.
  • the cycloalkynyl and heterocyclic alkynyl may be substituted or unsubstituted.
  • the cycloalkynyl and heterocyclic alkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo or thiol as described herein.
  • aryl refers to a group containing 60 or less carbon atoms of any carbon-based aromatic group, including but not limited to benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like.
  • the term “aryl” further includes “heteroaryl”, which is defined as a group containing an aromatic group having at least one heteroatom within a ring. Examples of heteroatoms include, but are not limited to, a nitrogen, oxygen, sulfur, or phosphorus atom.
  • aryl non-heteroaryl (which is also included in the term “aryl”) defines an aromatic-containing group that is free of heteroatoms.
  • the aryl may be substituted or unsubstituted.
  • the aryl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, sulfo-oxo or thiol as described herein.
  • a term “biaryl” is a particular type of aryl and is included in definition of “aryl”. The biaryl refers to two aryl joined together by a fused ring structure, as in naphthalene, or two aryl joined by one or more carbon-carbon bonds, as in biphenyl.
  • aldehyde as used herein is represented by a formula —C(O)H. Throughout this specification, “C(O)” is a short form of carbonyl (i.e., C ⁇ O).
  • amine or “amino” as used herein is represented by the formula —NR 1 R 2 , where R 1 and R 2 may independently be selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.
  • alkylamino as used herein is represented by a formula -NH(-alkyl), where the alkyl is as described in the present disclosure.
  • Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino, tert-butylamino, pentylamino, isopentylamino, tert-pentylamino, hexylamino and the like.
  • dialkylamino as used herein is represented by a formula —N(-alkyl) 2 , where the alkyl is as described in the present disclosure.
  • Representative example include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, dipentylamino, diisopentylamino, di-tert-pentylamino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino and the like.
  • a term “carboxylic acid” as used herein is represented by a formula —C(O)OH.
  • esters as used herein is represented by a formula —OC(O)R 1 or —C(O)OR 1 , where R 1 may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.
  • a term “polyester” as used herein is represented by a formula —(R 1 O(O)C—R 2 —C(O)O) a — or —(R 1 O(O)C—R 2 —OC(O)) a —, where R 1 and R 2 can independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein and “a” is an integer between 1 to 500.
  • the term “polyester” is used to describe groups produced by reaction between a compound having at least two carboxyl and a compound having at least two hydroxy.
  • ether as used herein is represented by a formula R 1 OR 2 , where R 1 and R 2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.
  • a term “polyether” as used herein is represented by a formula —(R 1 O—R 2 O) a —, where R 1 and R 2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein and “a” is an integer between 1 to 500.
  • polyether groups include polyethylene oxide, polypropylene oxide and polybutylene oxide.
  • halogen refers to halogen fluorine, chlorine, bromine and iodine.
  • heterocyclyl refers to monocyclic and polycyclic non-aromatic ring systems
  • heteroaryl refers to monocyclic and polycyclic aromatic ring systems of not more than 60 carbon atoms, where at least one of ring members is not carbon.
  • This term includes azetidinyl, dioxane, furyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl (oxazolyl including 1,2,3-oxadiazole, 1,2,5-oxadiazole and 1,3,4-oxadiazole), piperazinyl, piperidyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuran, tetrahydropyranyl, tetrazinyl including 1,2,4,5-tetrazinyl, tetrazolyl including 1,2,3,4-tetrazolyl and 1,2,4,5-tetrazolyl, thiadiazole including 1,2,3-thiadiazole, 1,2,5-thiadiazole and 1,3,4-thiadiazole,
  • hydroxyl as used herein is represented by a formula —OH.
  • ketone as used herein is represented by a formula R 1 C(O)R 2 , where R 1 and R 2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.
  • a term “azido” as used herein is represented by a formula —N 3 .
  • nitro as used herein is represented by a formula —NO 2 .
  • nitrile as used herein is represented by a formula —CN.
  • sil as used herein is represented by a formula —SiR 1 R 2 R 3 , where R 1 , R 2 and R 3 may independently be alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.
  • a term “sulfo-oxo” as used herein is represented by a formula —S(O)R 1 , —S(O) 2 R 1 , —OS(O) 2 R 1 or —OS(O) 2 OR 1 , where R1 may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.
  • S(O) is a short form of S ⁇ O.
  • a term “sulfonyl” as used herein refers to a sulfo-oxo represented a formula —S(O) 2 R 1 , where R 1 may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.
  • R 1 may be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl.
  • R 1 S(O)R 2 A term “sulfoxide” as used herein is represented by a formula R 1 S(O)R 2 , where R 1 and R 2 may independently be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl or heteroaryl as described herein.
  • thiol as used herein is represented by a formula —SH.
  • R 1 ”, “R 2 ”, “R 3 ”, “R n ” may independently have one or more of groups listed above.
  • R 1 is linear alkyl
  • one hydrogen atom of the alkyl may be optionally substituted with hydroxy, alkoxy, alkyl, halogen or the like.
  • a first group may be incorporated within a second group, or the first group may be side linked (i.e., connected) to the second group.
  • an alkyl including amino the amino may be incorporated within a main chain of the alkyl.
  • the amino may be linked to the main chain of the alkyl. Nature of the selected group may determine whether the first group is embedded in or linked to the second group.
  • the compound of that present disclosure may contain an “optionally substituted” moiety.
  • a term “substituted” (whether or not a term “optionally” exists before it) means that one or more hydrogen atoms of a given moiety are substituted with a suitable substituent.
  • an “optionally substituted” group may have suitable substituents at each of substitutable positions of the group, and when more than one position in any given structure may be substituted with more than one substituent selected from groups designated, the substituents may be the same or different at each position.
  • Combinations of substituents contemplated in the present disclosure are preferably combinations that form stable or chemically feasible compounds. It is also contemplated that in certain aspects, respective substituents may be further optionally substituted (i. e., further substituted or unsubstituted) unless explicitly stated to the contrary.
  • a structure of the compound may be represented by a following formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. are mentioned several times in chemical structures and units disclosed and described in this disclosure. Any description of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. in the specification is applicable to any structure or unit referring to R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , etc. respectively, unless otherwise specified.
  • fused ring means that two adjacent substituents may be fused to form a six-member aromatic ring, a heteroaromatic ring, such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a m-diazepine ring, and the like, as well as a saturated six or seven-member carbocyclic ring or carboheterocyclic ring, and the like.
  • a heteroaromatic ring such as a benzene ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a m-diazepine ring, and the like, as well as a saturated six or seven-member carbocyclic ring or carboheterocyclic ring, and the like.
  • both hydrogen and carbon nuclear magnetic resonance spectra were measured in deuterated chloroform (CDCl 3 ) or deuterated dimethyl sulfoxide (DMSO-d 6 ), in which the hydrogen spectra is made using a 400 or 500 MHz nuclear magnetic resonance spectrometer and the carbon spectra is made using a 100 or 126 MHz nuclear magnetic resonance spectrometer, with chemical shifts being based on tetramethylsilane (TMS) or residual solvent.
  • TMS tetramethylsilane
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 50:1 to 10:1 so as to obtain a product 1-Br, 5.60 g as a white solid, with a yield of 65%.
  • the sealed tube was placed in an oil bath at 110° C., stirred for reacting for 2 days, cooled to the room temperature, and then this mixture was washed with water, dilute hydrochloric acid was added to adjust to neutral or weak acid, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with an aqueous layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 90° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain the ligand (S, R)-LA1, 533 mg as white solid, with a yield of 70%.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 2 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (114 mg, 0.6 mmol, 2.0 equiv.) and dichloromethane (30 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 1:1 so as to obtain a product (S, R)-P-PtLA1, 126 mg as pale primrose solid, with a yield of 60%.
  • the sealed tube was placed in an oil bath at 100° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (R, S)-LA1, 2.12 g as a white solid, with a yield of 51%.
  • the sealed tube was placed in an oil bath at 100° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 120° C. for 2 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (30 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, dried with anhydrous sodium sulfate and filtered, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 90° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 110° C. for 2 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (140 mg, 0.74 mmol, 2.0 equiv.) and dichloromethane (30 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, dried with anhydrous sodium sulfate and filtered, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 100° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 100° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 758 mg white solid, with a yield of 71%.
  • P-PtLC1 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equiv.) and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (22 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 525 mg white solid, with a yield of 45%.
  • M-PtLC1 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equiv.) and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (22 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • the crude was separated and purified by a silica gel chromatography column with an eluent with a volume ratio of petroleum ether/dichloromethane being 4:1 to 2:1, so as to obtain a product (S, R)-P-PtLAN, 91 mg as red solid, with a yield of 37%.
  • this mixture was reacted with stirring in an oil bath at 110° C. for 25 hours, cooled to the room temperature, and the solvent was distilled off at a reduced pressure so as to obtain a crude.
  • the crude was separated and purified by a silica gel chromatography column with an eluent with a volume ratio of petroleum ether/ethyl acetate being 6:1 to 2:1, so as to obtain a product (R, S)-M-LAN, 608 mg as foamy solid, with a yield of 69%.
  • the crude was separated and purified by a silica gel chromatography column with an eluent with a volume ratio of petroleum ether/dichloromethane being 4:1 to 2:1, so as to obtain a product (R, S)-M-PtLAN, 127 mg as red solid, with a yield of 39%.
  • the sealed tube was placed in an oil bath at 90° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product L III-1, 431 mg as a white solid, with a yield of 56%.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 30:1 to 10:1, so as to obtain 353 mg white solid, with a yield of 37%.
  • M-PtLIII-1 (200 mg, 0.41 mmol, 1.0 equiv.), potassium chloroplatinate (178 mg, 0.43 mmol, 1.05 equiv.) and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (25 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 678 mg white solid, with a yield of 60%.
  • P-PtLB1 (200 mg, 0.41 mmol, 1.0 equiv.), potassium chloroplatinate (178 mg, 0.43 mmol, 1.05 equiv.) and tetra-n-butylammonium bromide (13 mg, 0.041 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (25 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 678 mg white solid, with a yield of 60%.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 20:1 to 10:1, so as to obtain 480 mg white solid, with a yield of 54%.
  • P-LD1 200 mg, 0.37 mmol, 1.0 equiv.
  • potassium chloroplatinate 162 mg, 0.39 mmol, 1.05 equiv.
  • tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (22 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 20:1 to 10:1, so as to obtain 433 mg white solid, with a yield of 49%.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 0.55 g white solid, with a yield of 62%.
  • P-PtLE1 (200 mg, 0.37 mmol, 1.0 equiv.), potassium chloroplatinate (162 mg, 0.39 mmol, 1.05 equiv.) and tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (22 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 444 mg white solid, with a yield of 48%.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 10:1 to 5:1, so as to obtain 455 mg white solid, with a yield of 47%.
  • P-LF1 200 mg, 0.37 mmol, 1.0 equiv.
  • potassium chloroplatinate 162 mg, 0.39 mmol, 1.05 equiv.
  • tetra-n-butylammonium bromide (12 mg, 0.037 mmol, 10 mol %) were sequentially added in a 50 mL three-necked flask with a magnetic rotor, and nitrogen was purged for three times, acetic acid (22 mL) was added, which was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, warmed again to 120° C. for reacting for 2 days.
  • reaction solution was washed with water and extracted with ethyl acetate for three times. Then organic phases were combined, washed once with water, dried with anhydrous sodium sulfate and filtered, mixed with silica gel, loaded in a dry manner, and separated and purified by column chromatography, with an eluant of petroleum ether:ethyl acetate of 15:1 to 8:1, so as to obtain 546 mg white solid, with a yield of 62%.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand P-B1, 430 mg as a white solid, with a yield of 53%.
  • P-PtB1 (243 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.63 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube, followed by nitrogen purge for three times and addition of acetic acid (36 mL) pre-purged with nitrogen.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 3 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand M-B1, 560 mg as a white solid, with a yield of 69%.
  • M-PtB1 (243 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.63 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube, followed by nitrogen purge for three times and addition of acetic acid (36 mL) pre-purged with nitrogen.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 3 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • ligand P-B2 1-Br (689 mg, 2.20 mmol, 1.1 equivalent), 1-OH (443 mg, 2.00 mmol, 1.0 equivalent) and cuprous iodide (76 mg, 0.40 mmol, 20 mol %), ligand 2 (69 mg, 0.20 mmol, 10 mol %) and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added into a dry sealed tube with a magnetic rotor. Nitrogen was purged for three times, and N, N-dimethylformamide (5 mL) was added under nitrogen protection.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand P-B2, 623 mg as a white solid, with a yield of 68%.
  • P-PtB2 (2) Synthesis of P-PtB2: P-B1 (182 mg, 0.40 mmol, 1.0 equiv.), potassium chloroplatinate (174 mg, 0.42 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (13 mg, 0.040 mmol, 0.1 equiv.) were sequentially added into a 50 mL dry three-necked flask with a magnetic rotor and a condenser tube, followed by nitrogen purge for three times and addition of acetic acid (24 mL) pre-purged with nitrogen.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 3 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (152 mg, 0.8 mmol, 2.0 equiv.) and dichloromethane (40 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand M-B2, 487 mg as a white solid, with a yield of 54%.
  • M-B2 (273 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.63 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube, followed by nitrogen purge for three times and addition of acetic acid (36 mL) pre-purged with nitrogen.
  • acetic acid 36 mL
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 3 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • ligand P-B2 1-Br (689 mg, 2.20 mmol, 1.1 equivalent), B3-OH (443 mg, 2.00 mmol, 1.0 equivalent) and cuprous iodide (76 mg, 0.40 mmol, 20 mol %), ligand 2 (69 mg, 0.20 mmol, 10 mol %) and potassium phosphate (849 mg, 4.00 mmol, 2.0 equiv.) were sequentially added into a dry sealed tube with a magnetic rotor. Nitrogen was purged for three times, and N, N-dimethylformamide (5 mL) was added under nitrogen protection.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand P-B3, 590 mg as a white solid, with a yield of 65%.
  • P-PtB3 (182 mg, 0.40 mmol, 1.0 equiv.), potassium chloroplatinate (174 mg, 0.42 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (13 mg, 0.040 mmol, 0.1 equiv.) were sequentially added into a 50 mL dry three-necked flask with a magnetic rotor and a condenser tube, followed by nitrogen purge for three times and addition of acetic acid (24 mL) pre-purged with nitrogen.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 3 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (152 mg, 0.8 mmol, 2.0 equiv.) and dichloromethane (40 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand M-B3, 590 mg as a white solid, with a yield of 64%.
  • M-B3 (273 mg, 0.60 mmol, 1.0 equiv.), potassium chloroplatinate (262 mg, 0.63 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (19 mg, 0.060 mmol, 0.1 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube, followed by nitrogen purge for three times and addition of acetic acid (36 mL) pre-purged with nitrogen.
  • acetic acid 36 mL
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 100° C. for 3 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride (228 mg, 1.2 mmol, 2.0 equiv.) and dichloromethane (60 mL) were added and stirred at the room temperature for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 80° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain M-B8, 1.05 g as white solid, with a yield of 50%.
  • M-B8 (1.0 g, 2.25 mmol, 1.0 equiv.) was sequentially added into a dry sealed tube with a magnetic rotor, and nitrogen was purged for three times, and toluene (30 mL) and methyl iodide (384 mg, 2.71 mmol, 1.2 equiv.) were added under nitrogen protection.
  • the sealed tube was stirred in an oil bath at 100° C. for reaction for 2 days, cooled to the room temperature, and filtered after adding water. The solid was transferred to the sealed tube and methanol (30 mL) was added.
  • M-PtB8 M-B8-Me (237 mg, 0.39 mmol, 1.0 equiv.), (1,5-cyclooctadiene) platinum dichloride (154 mg, 0.41 mmol, 1.05 equiv.) and sodium acetate (160 mg, 1.18 mmol, 3.0 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube. The nitrogen was purged for three times, and ethylene glycol dimethyl ether (25 mL) was added.
  • ligand P-B9 1-Br (500 mg, 1.60 mmol, 1.0 equivalent), B9-OH (301 mg, 1.60 mmol, 1.0 equivalent) and cuprous iodide (31 mg, 0.16 mmol, 10 mol %), ligand 2 (55 mg, 0.16 mmol, 10 mol %) and potassium phosphate (680 mg, 3.20 mmol, 2.0 equiv.) were sequentially added into a dry sealed tube with a magnetic rotor. Nitrogen was purged for three times, and N, N-dimethylformamide (10 mL) was added under nitrogen protection.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand P-B9, 526 mg as a white solid, with a yield of 78%.
  • P-PtB9 (200 mg, 0.48 mmol, 1.0 equiv.), potassium chloroplatinate (208 mg, 0.50 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (15 mg, 0.048 mmol, 0.1 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube, and nitrogen was purged for three times, acetic acid (30 mL) was added, the reaction solution was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, reacted at 110° C.
  • ligand M-B9 2-Br (500 mg, 1.60 mmol, 1.0 equivalent), B9-OH (301 mg, 1.60 mmol, 1.0 equivalent) and cuprous iodide (31 mg, 0.16 mmol, 10 mol %), ligand 2 (55 mg, 0.16 mmol, 10 mol %) and potassium phosphate (680 mg, 3.20 mmol, 2.0 equiv.) were sequentially added into a dry sealed tube with a magnetic rotor. Nitrogen was purged for three times, and N, N-dimethylformamide (10 mL) was added under nitrogen protection.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain ligand M-B9, 514 mg as a white solid, with a yield of 77%.
  • M-PtB9 (200 mg, 0.48 mmol, 1.0 equiv.), potassium chloroplatinate (208 mg, 0.50 mmol, 1.05 equiv.), tetra-n-butylammonium bromide (15 mg, 0.048 mmol, 0.1 equiv.) were sequentially added into a 100 mL dry three-necked flask with a magnetic rotor and a condenser tube, and nitrogen was purged for three times, acetic acid (30 mL) was added, the reaction solution was then bubbled with nitrogen for 30 minutes, stirred at the room temperature for 12 hours, reacted at 110° C.
  • This mixture was placed in an oil bath at 80° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (R, S)-LJ1, 182 mg as a white solid, with a yield of 30%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (S) L1, 475 mg as a white solid, with a yield of 39%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (R) L1, 549 mg as a white solid, with a yield of 45%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (S) L2, 450 mg as a white solid, with a yield of 46%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (R) L2, 421 mg as a white solid, with a yield of 43%.
  • the sealed tube was placed in an oil bath at 100° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the sealed tube was placed in an oil bath at 100° C., stirred for reacting for 2 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 10:1 to 5:1 so as to obtain a product (R) L3, 420 mg as a white solid, with a yield of 51%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 15:1 to 5:1 so as to obtain the ligand (S, R)-L-OO, 480 mg as black solid, with a yield of 54%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/ethyl acetate of 15:1 to 5:1 so as to obtain the ligand (R, S)-L-OO, 750 mg as yellow brown solid, with a yield of 84%.
  • reaction solution was bubbled with nitrogen for 30 minutes, it was stirred at the room temperature for 12 hours, and then was reacted with stirring at 120° C. for 2 days, cooled to the room temperature, and solvent was distilled off at a reduced pressure, and stannous chloride dihydrate (1.10 g, 5.00 mmol, 10.0 equiv.) and dichloromethane (15 mL) were added and stirred at 40° C. for 1 day.
  • the reaction solution was washed with water, the aqueous phase was extracted three times with dichloromethane, organic phases were combined, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 3:1 to 1:1 so as to obtain a product M-PtOO, 185 mg as pale primrose solid, with a yield of 60%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 3:1 to 1:1 so as to obtain the ligand (S, R)-L-OC, 305 mg as light brown solid, with a yield of 60%.
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 3:1 to 1:1 so as to obtain the ligand (R, S)-L-OC, 278 mg as light yellow solid, with a yield of 55%.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 2:1 to 1:1 so as to obtain a product M-PtOC, 80 mg as pale primrose solid, with a yield of 30%.
  • Example 50 synthesis of tetradentate cyclometalated platinum (II) complex P-PtS as follow
  • the sealed tube was placed in an oil bath at 85° C., stirred for reacting for 3 days, cooled to the room temperature, then sodium bicarbonate was added to adjust to weak base, ethyl acetate was added for extraction, with a water layer extracted with ethyl acetate for three times, then organic phases were combined, washed once with brine, dried with anhydrous sodium sulfate, and filtered, and solvent was distilled off at a reduced pressure.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 3:1 to 1:1 so as to obtain the ligand (S, R)-L-S, 650 mg as light brown solid, with a yield of 64%.
  • the crude was separated and purified by a silica gel chromatography column with an eluent of petroleum ether/dichloromethane of 4:1 to 2:1 so as to obtain a product P-PtS, 120 mg as pale primrose solid, with a yield of 28%.
  • 6-31G(d) baisc sets were used for C, H, O and N atoms, while LANL2DZ baisc sets were used for Pt atom.
  • the enantiomeric purity (ee value) was determined on a chiral column EnantiopakR-C (with a specification of 4.6 ⁇ 250 mm, 5 um).
  • FIG. 1 shows a design idea of an optically pure spiro chiral tetradentate cyclometalated platinum (II) and palladium (II) complex circularly polarized luminescence material with metal ion as a center: the optically pure raw materials are economical and easy to be obtained; spiro chirality can be generated by autonomous induction of central chirality; there's no need for chiral resolution for the circularly polarized luminescence material, which greatly saves preparation cost of the optical pure materials, and the circularly polarized luminescence material can be prepared in a large amount and is not limited by resolution of a chiral preparation column.
  • ligands containing central chirality can autonomously induce generation of M spiro chirality
  • ligands containing central chirality can autonomously induce generation of P spiro chirality
  • a M spiro chiral molecule and a P spiro chiral molecule are enantiomers to each other.
  • the luminescent color of the tetradentate metal complex can be efficiently adjusted approximately by adjusting the structure of the tetradentate ligand, and adjustment from an ultraviolet region at about 360 nm to a red region at 650 nm can be achieved, and it is believed that infrared luminescence can also be achieved through further regulation of the tetradentate ligand structure.
  • emission spectra from FIG. 6 to FIG. 20 are substantially completely coincident, which further proves that corresponding material molecules in the figures are enantiomers.
  • FIGS. 26 to 33 are circularly polarized luminescence spectra of part of material molecules.
  • the comparative material molecules PtON1, PtON3 and PtOO3 have no circularly polarized luminescence.
  • the material has high chemical stability and thermal stability.
  • the designed and developed tetradentate ligand can well coordinate with dsp 2 hybridized platinum (II) and palladium (II) metal ions to form molecules with a stable and rigid quadrilateral configuration, with high chemical stability; meanwhile, since large steric hindrance effect exists between the designed central chiral ligand L a and the ligand L 1 or L b at another end, the metal complex molecule as a whole can form a stable spiro chiral tetradentate cyclometalated complex, so that the spiro chiral tetradentate cyclometalated complex can not be racemized and lose circularly polarized luminescence property in a solution or in a process of sublimation at a high temperature.
  • MLCT metal-to-ligand charge transfer states
  • ILCT intra-ligand charge transfer
  • an organic light emitting device carriers are injected into a luminescent material from positive and negative electrodes to generate a luminescent material at an excited state and cause it to illuminate.
  • the complex of the present disclosure represented by the general formula (1) can be applied as a phosphorescent luminescent material to an excellent organic light emitting device such as an organic photoluminescent element or an organic electroluminescent element.
  • the organic photoluminescence element has a structure in which at least a light-emitting layer is formed on a substrate.
  • the organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed.
  • the organic layer includes at least a light-emitting layer and may be composed of only the light-emitting layer or may have more than one organic layer in addition to the light-emitting layer.
  • Example of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer, and the like.
  • the hole transport layer may be a hole injection and transport layer having a hole injection function
  • the electron transport layer may be an electron injection and transport layer having an electron injection function.
  • the substrate, the anode, the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the cathode are sequentially shown, where the light-emitting layer is a mixed layer in which a guest material is doped into a host material.
  • ITO/HATCN (10 nm)/TAPC (65 nm)/host material: luminescent material (10 wt. %, 20 nm)/TmPyPB (55 nm)/LiF/A1.
  • ITO represents a transparent anode
  • HATCN represents the hole injection layer
  • TAPC represents the hole transport layer
  • the host material is mCBP and 26mCPy, respectively.
  • TmPyPB represents the electron transport layer
  • LiF represents the electron injection layer
  • Al represents the cathode. Numbers in nanometer (nm) in parentheses are thicknesses of films.
  • a molecular formula of the material used in the device is as follows:
  • an organic light emitting device carriers are injected into a luminescent material from positive and negative electrodes to generate a luminescent material at an excited state and cause it to illuminate.
  • the complex of the present disclosure can be applied as a phosphorescent luminescent material to an excellent organic light emitting device such as an organic photoluminescent element or an organic electroluminescent element.
  • the organic photoluminescence device has a structure in which at least a light-emitting layer is formed on a substrate.
  • the organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed.
  • the organic layer includes at least a light-emitting layer and may be composed of only the light-emitting layer or may have more than one organic layer in addition to the light-emitting layer.
  • Example of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, an exciton blocking layer, and the like.
  • the hole transport layer may be a hole injection and transport layer having a hole injection function
  • the electron transport layer may be an electron injection and transport layer having an electron injection function.
  • FIG. 6 a structure of the organic light emitting device is schematically shown in FIG. 6 . In FIG.
  • the substrate, the anode, the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the cathode are sequentially shown, where the light-emitting layer is a mixed layer in which a guest material is doped into a host material.
  • Respective layers of the organic light emitting device of the present disclosure may be formed by methods such as vacuum evaporation, sputtering, ion plating, or can be formed in a wet manner such as spin coating, printing, Screen Printing, and the like, and solvent used is not specifically limited.
  • an OLED device of the present disclosure contains a hole transport layer
  • a hole transport material may preferably be selected from known or unknown materials, particularly preferably from following structures, which does not imply that the present disclosure is limited to the following structures:
  • the OLED device of the present disclosure contains a hole transport layer comprising one or more p-type dopants.
  • a preferred p-type dopant of the present disclosure is of following structures, which does not imply that the present disclosure is limited to the following structures:
  • the electron transport layer may be selected from at least one of compounds ET-1 to ET-13, which does not imply that the present disclosure is limited to following structures:
  • the electron transport layer may be formed of an organic material in combination with one or more n-type dopants such as LiQ.
  • the compound represented in example 1 was applied to an OLED device as a circularly polarized luminescence material, with a structure also being expressed as: on ITO-containing glass, a hole injection layer (HIL) of HT-1:P-3 (95:5 v/v), with a thickness of 10 nm; a hole transport layer (HTL) of HT-1, with a thickness of 90 nm; an electron blocking layer (EBL) of HT-10, with a thickness of 10 nm; a light-emitting layer (EML) of the host material (H-1 or H-2 or H-3 or H-4 or H-5 or H-6): the platinum metal complex of the present disclosure (95:5 v/v), with a thickness of 35 nm; an electron transport layer (ETL) of ET-13: LiQ (50:50 v/v), with a thickness of 35 nm; and then a 70 nm vapor-deposited cathode Al.
  • HIL hole injection layer
  • HTL hole transport layer
  • the fabricated organic light emitting device was tested at a current of 10 mA/cm 2 using standard methods well known in the art, in which a device with (S, R)-P-PtLAT as the luminescent material had a significant circularly polarized electroluminescent signal, with an asymmetry factor (g EL ) of up to 1.4 ⁇ 10 3 and a maximum external quantum efficiency (EQE) of up to 18%.
  • g EL asymmetry factor
  • EQE maximum external quantum efficiency
  • the structure is an example of application of the circularly polarized luminescence material of the present disclosure and does not limit a specific structure of the OLED device of the circularly polarized luminescence material of the present disclosure, and the circularly polarized luminescence material is not limited to the compounds represented in the examples.
  • the structure is an example of application of the phosphorescent material of the present disclosure and does not limit a specific structure of the OLED device of the phosphorescent material of the present disclosure, and the phosphorescent material is not limited to the compounds represented in the examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
US18/484,200 2021-04-15 2023-10-10 Central chirality induced spiro chiral tetradentate cyclometalated platinum (ii) and palladium (ii) complex-based circularly polarized luminescence material and application thereof Pending US20240059962A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN202110403546.1A CN115215852A (zh) 2021-04-15 2021-04-15 中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用
CN202110403546.1 2021-04-15
PCT/CN2022/086993 WO2022218399A1 (zh) 2021-04-15 2022-04-15 中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/086993 Continuation WO2022218399A1 (zh) 2021-04-15 2022-04-15 中心手性诱导螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用

Publications (1)

Publication Number Publication Date
US20240059962A1 true US20240059962A1 (en) 2024-02-22

Family

ID=83604558

Family Applications (1)

Application Number Title Priority Date Filing Date
US18/484,200 Pending US20240059962A1 (en) 2021-04-15 2023-10-10 Central chirality induced spiro chiral tetradentate cyclometalated platinum (ii) and palladium (ii) complex-based circularly polarized luminescence material and application thereof

Country Status (6)

Country Link
US (1) US20240059962A1 (zh)
EP (1) EP4306521A1 (zh)
JP (1) JP2024516580A (zh)
KR (1) KR20240016952A (zh)
CN (1) CN115215852A (zh)
WO (1) WO2022218399A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024093320A1 (zh) * 2022-11-04 2024-05-10 浙江工业大学 配合物、其应用、有机发光元件、及装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9882150B2 (en) * 2012-09-24 2018-01-30 Arizona Board Of Regents For And On Behalf Of Arizona State University Metal compounds, methods, and uses thereof
CN110003279A (zh) * 2013-06-10 2019-07-12 代表亚利桑那大学的亚利桑那校董会 具有改进的发射光谱的磷光四齿金属络合物
JP6804823B2 (ja) * 2013-10-14 2020-12-23 アリゾナ・ボード・オブ・リージェンツ・オン・ビハーフ・オブ・アリゾナ・ステイト・ユニバーシティーＡｒｉｚｏｎａ Ｂｏａｒｄ ｏｆ Ｒｅｇｅｎｔｓ ｏｎ ｂｅｈａｌｆ ｏｆ Ａｒｉｚｏｎａ Ｓｔａｔｅ Ｕｎｉｖｅｒｓｉｔｙ 白金錯体およびデバイス
US10020455B2 (en) * 2014-01-07 2018-07-10 Arizona Board Of Regents On Behalf Of Arizona State University Tetradentate platinum and palladium complex emitters containing phenyl-pyrazole and its analogues
US11552261B2 (en) * 2017-06-23 2023-01-10 Universal Display Corporation Organic electroluminescent materials and devices

Also Published As

Publication number Publication date
JP2024516580A (ja) 2024-04-16
WO2022218399A1 (zh) 2022-10-20
EP4306521A1 (en) 2024-01-17
CN115215852A (zh) 2022-10-21
KR20240016952A (ko) 2024-02-06

Similar Documents

Publication Publication Date Title
US20230322833A1 (en) Metal-assisted delayed fluorescent emitters employing pyrido-pyrrolo-acridine and analogues
US10056564B2 (en) Tetradentate metal complexes containing indoloacridine and its analogues
US20230015063A1 (en) Metal-assisted delayed fluorescent emitters containing tridentate ligands
US20210047296A1 (en) Non-platinum metal complexes for excimer based single dopant white organic light emitting diodes
US11472827B2 (en) Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues
US10930865B2 (en) Tetradentate platinum (II) and palladium (II) complexes, devices, and uses thereof
US9318712B2 (en) Xanthone compound and organic light-emitting device including the same
US20190372024A1 (en) Novel heterocyclic compound and organic light emitting device using the same
US9735376B2 (en) Organometallic compound and organic light-emitting device including the same
US20240059962A1 (en) Central chirality induced spiro chiral tetradentate cyclometalated platinum (ii) and palladium (ii) complex-based circularly polarized luminescence material and application thereof
WO2024027411A1 (zh) 一种圆偏振发光材料及应用、发光显示器件及显示装置
US20240164204A1 (en) Tetradentate cyclometalated platinum (ii) and palladium (ii) complex luminescence material containing quinoline structure unit and application thereof
US20160028024A1 (en) Organometallic compound and organic light-emitting device including the same
US10889605B2 (en) Phenyl-carbazole based tetradentate cyclometalated platinum complex and application thereof
WO2024093320A1 (zh) 配合物、其应用、有机发光元件、及装置
CN115594722B (zh) 配合物、其应用、有机发光元件、及装置
US11495711B2 (en) Device comprising organometallic complex luminescent material
CN116425803A (zh) 一种中心手性诱导螺手性四齿环金属铂(ii)配合物、电子器件及应用
CN116969998A (zh) 基于咔唑配位的螺手性四齿环金属铂(ii)和钯(ii)配合物圆偏振发光材料及应用

Legal Events

Date Code Title Description
STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION